EP0645175B1 - Entretoise pour des cellules de dialyse, d'électrodialyse ou d'électrolyse - Google Patents

Entretoise pour des cellules de dialyse, d'électrodialyse ou d'électrolyse Download PDF

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Publication number
EP0645175B1
EP0645175B1 EP94114171A EP94114171A EP0645175B1 EP 0645175 B1 EP0645175 B1 EP 0645175B1 EP 94114171 A EP94114171 A EP 94114171A EP 94114171 A EP94114171 A EP 94114171A EP 0645175 B1 EP0645175 B1 EP 0645175B1
Authority
EP
European Patent Office
Prior art keywords
fibres
groups
several
spacer
hollow
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP94114171A
Other languages
German (de)
English (en)
Other versions
EP0645175A1 (fr
Inventor
Bernd Dipl.-Chem. Bauer
Thomas Dipl.-Ing. Menzel
Petra Dipl.-Ing. Kehl
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
Original Assignee
Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
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Publication of EP0645175A1 publication Critical patent/EP0645175A1/fr
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Anticipated expiration legal-status Critical
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/10—Supported membranes; Membrane supports
    • B01D69/107—Organic support material
    • B01D69/1071—Woven, non-woven or net mesh
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
    • B01D61/44—Ion-selective electrodialysis
    • B01D61/445—Ion-selective electrodialysis with bipolar membranes; Water splitting
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
    • B01D61/44—Ion-selective electrodialysis
    • B01D61/46—Apparatus therefor
    • B01D61/48—Apparatus therefor having one or more compartments filled with ion-exchange material, e.g. electrodeionisation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
    • B01D61/44—Ion-selective electrodialysis
    • B01D61/46—Apparatus therefor
    • B01D61/50—Stacks of the plate-and-frame type
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
    • B01D63/08—Flat membrane modules
    • B01D63/082—Flat membrane modules comprising a stack of flat membranes
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B13/00—Diaphragms; Spacing elements

Definitions

  • the invention relates to ion-conductive spacers for dialysis, electrodialysis or electrolysis cells.
  • electrodialysis is always the goal, a diluate and a concentrate from a raw solution to create, both diluate and concentrate as a product stream can be viewed.
  • Desalination e.g. in brackish water desalination, in the softening of boiler water or process water, in which Demineralization of tap water, or in the separation of heavy metals from process water in galvanic baths to consider the diluate as a product stream.
  • This is general striving for maximum depletion.
  • This leads to a decrease in the electrical conductivity of the diluate circuit and an increase in electrical resistance.
  • the process costs increase with increasing desalination and the maximum allowed current densities decrease from what an increase in investment costs (membrane costs) results.
  • the cell resistance is determined by the resistance of the membranes, the diluate chamber and the boundary layer and through the shielding effect the spacer determines.
  • Diluate concentrations in Diluate
  • a decrease in polarization is however through a reduction in current density is achievable, and is achieved by enables the use of ion-conductive spacers.
  • the main effect seems to be from an enlargement of the Surface between ion exchange membranes and the solution to result.
  • the thickness of the laminar boundary layer can be reduced.
  • the laminar boundary layer is depleted in systems with ion-conductive spacers in the same way, however in contrast to conventional electrodialysis the current distributed over a larger surface, and thus the current density decreased. The limit current is thus through the entire Spacer area and the thickness of the laminar layer around the Spacer determined.
  • an ion-conductive spacer it can be used for Boiler feed water desalination to less than 25 ppm total ion content can be achieved.
  • Kedem et al. describe in "EDS - Sealed Cell Electrolysis" a method of making with anion exchange resin filled pockets made of polyethylene membranes.
  • the welded Unit consists of a 0.4 mm thick spacer between two heterogeneous PE membranes.
  • the disadvantage of these bags is that the hydrodynamics is insufficient, so that no isotropic flow through the ion exchanger packing guaranteed and also a high pressure drop must be accepted through the Chamber.
  • Ion exchange resins typically have large volume changes due to a load-dependent swelling, which in the welded pockets cannot be compensated.
  • FR-A-2292504 describes a material which is a sulfochlorinated or hydrolyzed aminated fabric made of polyethylene threads represents. This material has ionic conductivity Properties, but it is not apparent from the document, that the threads are porous.
  • spacers are designed to be general and lightweight feasible production process can be produced.
  • the membrane area A apparently increases and thus the total resistance R reduced.
  • Preferred embodiments of the spacers according to the invention have pore diameters between 80 and 180 ⁇ , and / or thicknesses between 3 ⁇ 10 -3 and 5 ⁇ 10 -4 m.
  • Spacers are made of ceramic or an organic polymer, thermoplastic polymers being particularly preferred are. Without restricting generality, are preferred organic polymers polypropylene, polyethylene, polysulfone, Polyether sulfone, polyphenylene oxide, polyphenylene sulfide, polyether ketone, Polyether ether ketone, polyether ether ketone ketone, Polystyrene or a mixture thereof.
  • Spacers contain weakly basic secondary groups as anionic groups or tertiary amino groups, strongly basic quaternary Ammonium groups, strongly basic quaternary phosphonium groups or tertiary sulfonium groups or a mixture thereof.
  • Spacers are the cationic groups of strongly acidic sulfonic acid groups or methylene sulfonic acid groups, weak acid carboxyl groups or phosphonium groups, acid arsenic or acidic selenic groups or a mixture thereof.
  • the spacers according to the invention can be made from hollow fiber membranes consist of the known methods with anionic and / or cationic groups have been modified and become one Tissues are processed.
  • the spacers according to the invention can be one with anionic ones and / or modified tissue cationic groups be made of porous and / or non-porous polymer threads and / or hollow threads.
  • the spacers according to the invention are made of porous and / or non-porous polymer threads and / or polymer hollow threads consist of the known methods with anionic and / or cationic groups have been modified and are processed into a fabric.
  • spacers according to the invention exist made of a porous polymer film using known methods modified with anionic and / or cationic groups is.
  • porous filtration membranes according to known Methods modified with anionic and / or cationic groups and can be used according to the invention as a spacer.
  • these are outside the effective membrane area with a Seal provided, which is preferably made of an elastomer a transfer tape, or from a thermoplastic polymer consists.
  • the spacers according to the invention can be produced in a variety of ways Way happen. So it is e.g. possible, Hollow fiber membranes by known methods with anionic and / or modify cationic groups and then these to be processed into a fabric according to usual methods.
  • thermoplastic Polymers from the group of olefinic polymers, the condensation and oxidation polymers by thermal Precipitation into threads or hollow threads by known methods be deformed. These threads or hollow threads are then by conventional methods with anionic and / or cationic Modified groups, and the modified threads or hollow threads processed into fabrics.
  • thermoplastic polymers from the group of olefinic Polymers, condensation and oxidation polymers thermal precipitation to known threads or To deform hollow threads, the resulting threads or hollow threads to process tissues, and the resulting tissues by conventional methods with anionic and / or cationic Modify groups.
  • thermoplastic polymers with the addition of pore-forming Components are carried out.
  • pore-forming Components are characterized by a temperature-dependent Mixing gap in the binary phase diagram with the polymer off, i.e. they are e.g. homogeneous at elevated temperature miscible with the polymer melt, but separate when cooling above the melting point.
  • the pore formers should be thermally stable up to the extrusion temperature and opposite be chemically inert to the polymer.
  • polypropylene and polyethylene are e.g. Paraffins, fatty amines and higher molecular weight Suitable for soaps.
  • thermoplastic polymers or mixtures thereof are used be or already with anionic and / or with cationic Groups of modified thermoplastic polymers, each made from the group of olefinic polymers, condensation and of the oxidation polymers.
  • the resulting polymer film is then used by conventional methods with anionic and / or with cationic Modified groups.
  • porous filtration membranes according to known Process with anionic and / or with cationic Modify groups.
  • the spacers according to the invention can be used in electrolysis cells be used.
  • conventional electrolysis causes gas bubbles to form on electrode surfaces or grids often have undesirable side effects.
  • a growing single bubble leads to a significant one Increase in voltage drop and thus to local Formation of thermal gradients, which, if not degraded burns can result in "hot spots".
  • These bubbles grow faster at higher current densities and at higher temperatures, with faster bubble growth causes a larger peeling radius.
  • a PP microfiltration hollow fiber membrane (Accurel® from ENKA) becomes an ion exchange membrane through sulfochlorination functionalized and processed into a fabric.
  • a 17% solution of polyether sulfone with sulfonated polyether ether ketone (1.10 meq ⁇ g -1 ) in a ratio of 1: 1 in N-methylpyrrolidone with propionic acid (2: 1) is spun into a thread or hollow thread and coagulated in water. Further processing takes place on a weaving machine.
  • DABCO 1,4-diazabicyclo [2.2.2] octane
  • a 15% solution of radically side chain brominated Polyphenylene oxide in N-methylpyrrolidone becomes a thread or hollow fiber spun and coagulated in water. After that the porous material in an aqueous solution of DABCO (1,4-diazabicyclo [2.2.2] octane) quaternized. Further processing takes place on a weaving machine.
  • DABCO 1,4-diazabicyclo [2.2.2] octane
  • a 16% solution of sulfonated polyether ether ketone (0.75 meq ⁇ g -1 ) in N-methylpyrrolidone is spun into a thread or hollow thread and coagulated in water. Further processing takes place on a weaving machine.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Water Supply & Treatment (AREA)
  • Health & Medical Sciences (AREA)
  • Urology & Nephrology (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)

Claims (17)

  1. Entretoise ioniquement conductrice pour des cellules de dialyse, d'électrodialyse ou d'électrolyse sous la forme d'une structure plane poreuse, qui présente une épaisseur comprise entre 10-2 et 10-4 m et qui est constituée d'une toile fonctionnalisée avec des groupes anioniques et/ou cationiques,
    caractérisée en ce que
    la toile présente des fils de polymère poreux et/ou des membranes à fibres creuses comprises entre 1 et 100 nm.
  2. Entretoise selon la revendication 1,
    caractérisée en ce que
    les diamètres de pores sont compris entre 8 et 18 nm.
  3. Entretoise selon la revendication 1 ou 2,
    caractérisée en ce que
    l'épaisseur est comprise entre 3.10-3 et 5.10-4 nm.
  4. Entretoise selon l'une ou plusieurs des revendications 1 à 3,
    caractérisée en ce que
    le polymère est un polymère thermoplastique.
  5. Entretoise selon la revendication 4,
    caractérisée en ce que
    le polymère est un polypropylène, un polyéthylène, une polysulfone, un polyéthersulfone, un polyphénylèneoxyde, un polyphénylènesulfure, un polyéthercétone, un polyétheréthercétone, un polyétheréthercétonecétone, un polystyrène ou un de leurs mélanges.
  6. Entretoise selon l'une ou plusieurs des revendications 1 à 5,
    caractérisée en ce que
    les groupes anioniques sont des groupes amino secondaires et/ou tertiaires faiblement basiques et/ou des groupes d'ammonium quaternaire fortement basiques et/ou des groupes de phosphonium quaternaires fortement basiques et/ou des groupes sulfonium tertiaires.
  7. Entretoise selon l'une ou plusieurs des revendications 1 à 6,
    caractérisée en ce que
    les groupes cationiques sont des groupes d'acide sulfurique fortement acides et/ou des groupes méthylènesulfoniques et/ou des groupes carboxyles faiblement acides et/ou des groupes phosphonium et/ou des groupes acides arséniques et/ou des groupes acides sélénoiques.
  8. Entretoise selon l'une ou plusieurs des revendications 1 à 7,
    caractérisée en ce qu'
    elle est munie d'un joint, en dehors de la surface efficace de membrane.
  9. Entretoise selon la revendication 8,
    caractérisée en ce que
    le joint est en élastomère.
  10. Entretoise selon la revendication 8,
    caractérisée en ce que
    le joint est un ruban adhésif transfert.
  11. Entretoise selon la revendication 8,
    caractérisée en ce que
    le point est en polymère thermoplastique.
  12. Procédé de fabrication d'entretoises selon l'une ou plusieurs des revendications 1 à 11,
    caractérisé en ce qu'
    on modifie des membranes de fibres creuses à diamètres de pores compris entre 1 et 100 nm selon des procédés connus avec des groupes anioniques et/ou cationiques et qu'on transforme les membranes à fibres creuses modifiées en une toile qui a une épaisseur comprise entre 10-2 et 10-4 m.
  13. Procédé de production d'entretoises selon l'une ou plusieurs des revendications 1 à 11,
    caractérisé en ce qu'
    on transforme des membranes à fibres creuses à diamètres de pores compris entre 1 et 100 nm en une toile ayant une épaisseur comprise entre 10-2 et 10-4 m et qu'on modifie la toile selon des procédés connus avec des groupes anioniques et/ou cationiques.
  14. Procédé de production d'entretoises selon l'une ou plusieurs des revendications 1 à 11,
    caractérisé en ce qu'
    on forme un mélange d'un ou plusieurs polymères thermoplastiques du groupe des polymères oléfiniques, des polymères de condensation et d'oxydation par précipitation thermique en fils ou en fils creux ayant des diamètres de pores compris entre 1 et 100 nm, qu'on modifie les fils ou fils creux selon des procédés connus avec des groupes anioniques et/ou cationiques et qu'on transforme les fils ou les fils creux modifiés en une toile ayant une épaisseur comprise entre 10-2 et 10-4 m.
  15. Procédé de production d'entretoises selon l'une ou plusieurs des revendications 1 à 11,
    caractérisé en ce qu'
    on forme un mélange d'un ou plusieurs polymères thermoplastiques du groupe des polymères oléfiniques, des polymères de condensation et d'oxydation par précipitation thermique en fils ou fils creux avec des diamètres de pores compris entre 1 et 100 nm, qu'on transforme les fils ou fils creux en une toile ayant une épaisseur comprise entre 10-2 et 10-4 m et qu'on modifie la toile selon des procédés connus avec des groupes anioniques et/ou cationique.
  16. Procédé de production d'entretoises selon l'une ou plusieurs des revendications 1 à 11,
    caractérisé en ce qu'
    on forme un mélange d'un ou plusieurs polymères thermoplastiques modifiés par des groupes anioniques et/ou cationiques du groupe des polymères oléfiniques, des polymères de condensation et d'oxydation par précipitation thermique en fils ou fils creux avec des diamètres de pores compris entre 1 et 100 nm, qu'on transforme les fils ou fils creux en une toile ayant une épaisseur comprise entre 10-2 et 10-4 m.
  17. Procédé selon la revendication 14, 15 ou 16,
    caractérisé en ce qu'
    on transforme les polymères thermoplastiques en ajoutant des composants formant des pores.
EP94114171A 1993-09-28 1994-09-09 Entretoise pour des cellules de dialyse, d'électrodialyse ou d'électrolyse Expired - Lifetime EP0645175B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4333020A DE4333020C2 (de) 1993-09-28 1993-09-28 Abstandhalter (Spacer) für Dialyse-, Elektrodialyse- oder Elektrolyse-Zellen und Verfahren zu deren Herstellung
DE4333020 1993-09-28

Publications (2)

Publication Number Publication Date
EP0645175A1 EP0645175A1 (fr) 1995-03-29
EP0645175B1 true EP0645175B1 (fr) 1998-12-23

Family

ID=6498856

Family Applications (1)

Application Number Title Priority Date Filing Date
EP94114171A Expired - Lifetime EP0645175B1 (fr) 1993-09-28 1994-09-09 Entretoise pour des cellules de dialyse, d'électrodialyse ou d'électrolyse

Country Status (3)

Country Link
EP (1) EP0645175B1 (fr)
AT (1) ATE174810T1 (fr)
DE (2) DE4333020C2 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102005003527A1 (de) * 2005-01-25 2006-07-27 Uhdenora S.P.A. Elektrolysezelle mit erweiterter aktiver Membranfläche
US8722839B2 (en) 2012-06-04 2014-05-13 Sabic Innovative Plastics Ip B.V. Poly(phenylene ether) fiber and method of making

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB877239A (en) * 1957-12-24 1961-09-13 Permutit Co Ltd Improvements relating to electrodialytic cells
NL259158A (fr) * 1959-12-17
CH586059A5 (fr) * 1974-11-29 1977-03-31 Yeda Res & Dev
US4465573A (en) * 1981-05-12 1984-08-14 Hare Harry M O Method and apparatus for the purification of water
US4804451A (en) * 1986-10-01 1989-02-14 Millipore Corporation Depletion compartment for deionization apparatus and method
DE69204187T2 (de) * 1991-03-13 1996-01-25 Ebara Corp Elektrisch regenerierbare Entmineralisierungsvorrichtung.

Also Published As

Publication number Publication date
EP0645175A1 (fr) 1995-03-29
ATE174810T1 (de) 1999-01-15
DE4333020C2 (de) 1997-02-06
DE4333020A1 (de) 1995-03-30
DE59407526D1 (de) 1999-02-04

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